Formation of chemically active chlorine compounds by reactions of atmospheric NaCl particles with gaseous N2O5 and ClONO2

Finlayson-Pitts, Barbara J.; Ezell, M. J.; Pitts, James N.

doi:10.1038/337241a0

Cited by 412 publications

(384 citation statements)

References 26 publications

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] The particle composition has been observed to range from no Cl À depletion (fresh sea salt) to complete Cl À depletion (heavily processed sea salt), and a strong anticorrelation of Cl À with NO 3 À has been reported. 4,7,8 As a result, the ratio of Cl À to NO 3 À in sea salt-derived aerosol decreases as air masses move downwind in coastal urban regions.…”

Section: Introductionmentioning

confidence: 99%

“…4,7,8 As a result, the ratio of Cl À to NO 3 À in sea salt-derived aerosol decreases as air masses move downwind in coastal urban regions. While nitrate ions are often treated as a stable end product of this chemistry, NO 3 À absorbs light in the actinic region above 290 nm and photodissociates via two reaction channels: 16 NO…”

Section: Introductionmentioning

confidence: 99%

“…28 These results suggest that the overlap of the nitrate absorption spectrum with solar radiation may decrease at the concentrations likely to be found in aerosols. However, it is not known how the UV absorption spectrum of NO 3 À is affected by the presence of Cl À , such as in processed sea salt particles. Molecular dynamics (MD) simulations provide a fundamental understanding of the interactions of ions with their solvent at the atomic level.…”

Section: Introductionmentioning

confidence: 99%

“…[29][30][31][32] These simulations have been applied to understanding surface-active mechanisms for halogen formation from sea salt aerosols [32][33][34][35][36] and other physicochemical processes at air-water interfaces with very good experimental agreement. 31,[37][38][39][40][41] Recent simulations show that nitrate ions in larger particles appear to reside below the interface in pure aqueous NaNO 3 and Mg(NO 3 ) 2 solutions with no particular preference to be solvated at surface. [42][43][44] However, the small number of nitrate ions that do reside near the interface in pure NaNO 3 solutions are under-coordinated by water molecules.…”

Section: Introductionmentioning

confidence: 99%

“…The authors suggested that the presence of Cl À enhances NO 3 À photolysis through formation of the NOCl intermediate and proposed that the photolysis of nitrate could oxidize halides in marine aerosols. More recently, UV irradiation of particles collected in marine environments has shown that NO 3 À photolysis is a major source of OH radicals in such particles. 55,56 The present studies describe the generation of gaseous NO 2 upon irradiation of deliquesced NaNO 3 compared to mixtures of NaCl and NaNO 3 deposited on a Teflon s substrate.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced surface photochemistry in chloride–nitrate ion mixtures

Wingen

Moskun

Johnson

et al. 2008

Phys. Chem. Chem. Phys.

116

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Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen lead to replacement of chloride ion by nitrate ion. Studies of the photochemistry of a model system were carried out using deliquesced mixtures of NaCl and NaNO 3 on a Teflon s substrate. Varying molar ratios of NaCl to NaNO 3 (1 : 9 Cl À : NO 3 À , 1 : 1 Cl À : NO 3 À , 3 : 1 Cl À : NO 3 À , 9 : 1 Cl À : NO 3 À) and NaNO 3 at the same total concentration were irradiated in air at 299 AE 3 K and at a relative humidity of 75 AE 8% using broadband UVB light (270-380 nm). Gaseous NO 2 production was measured as a function of time using a chemiluminescence NO y detector. Surprisingly, an enhanced yield of NO 2 was observed as the chloride to nitrate ratio increased. Molecular dynamics (MD) simulations show that as the Cl À : NO 3 À ratio increases, the nitrate ions are drawn closer to the interface due to the existence of a double layer of interfacial Cl À and subsurface Na + . This leads to a decreased solvent cage effect when the nitrate ion photodissociates to NO 2 +O À , increasing the effective quantum yield and hence the production of gaseous NO 2 . The implications of enhanced NO 2 and likely OH production as sea salt aerosols become processed in the atmosphere are discussed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Wingen

Moskun

Johnson

et al. 2008

Phys. Chem. Chem. Phys.

116

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Importance of tropospheric ClNO₂ chemistry across the Northern Hemisphere

Sarwar

Simon

Xing

et al. 2014

Geophys. Res. Lett.

131

198

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Laboratory and field experiments have revealed that uptake of dinitrogen pentoxide (N2O5) on aerosols containing chloride produces nitryl chloride (ClNO2) and nitric acid. We incorporate heterogeneous ClNO2 formation into the hemispheric Community Multiscale Air Quality model. This heterogeneous chemistry substantially enhances ClNO2 levels in several areas of the Northern Hemisphere and alters the composition of airborne reactive nitrogen, comprising more than 15% of monthly mean values in some areas. Model results suggest that this heterogeneous chemistry reduces monthly mean total nitrate by up to 25% and enhances monthly mean daily maximum 8 h ozone by up to 7.0 ppbv. The pathway also enhances hydroxyl radical by more than 20% in some locations which in turn increases sulfate and other secondary pollutants. The largest ClNO2 concentrations and impacts occur over China and Western Europe, two areas in which few relevant field measurements have been made.

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Origins of aerosol chlorine during winter over north central Colorado, USA

et al. 2015

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The Nitrogen, Aerosol Composition, and Halogens on a Tall Tower campaign (February-March 2011) , and presumably associated Cl À , originated from non-sea-salt sources. The heterogeneous chemical composition of saline soils throughout the western U.S., along with the nonlinearity of wind-driven soil deflation as a function of various surface soil properties, precludes a quantitative apportionment of soil, marine, and anthropogenic sources to the observed coarse-fraction aerosol. Nonetheless, results suggest that deflation of saline soils was a potentially important source of particulate Cl À that sustained atmospheric ClNO 2 production and associated impacts on oxidation processes over northern Colorado.

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Formation of chemically active chlorine compounds by reactions of atmospheric NaCl particles with gaseous N2O5 and ClONO2

Cited by 412 publications

References 26 publications

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Importance of tropospheric ClNO₂ chemistry across the Northern Hemisphere

Origins of aerosol chlorine during winter over north central Colorado, USA

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Formation of chemically active chlorine compounds by reactions of atmospheric NaCl particles with gaseous N2O5 and ClONO2

Cited by 412 publications

References 26 publications

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Importance of tropospheric ClNO2 chemistry across the Northern Hemisphere

Origins of aerosol chlorine during winter over north central Colorado, USA

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Importance of tropospheric ClNO₂ chemistry across the Northern Hemisphere